CA2383566A1 - Terpolymers and rubber mixtures containing special mineral oils - Google Patents
Terpolymers and rubber mixtures containing special mineral oils Download PDFInfo
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- CA2383566A1 CA2383566A1 CA002383566A CA2383566A CA2383566A1 CA 2383566 A1 CA2383566 A1 CA 2383566A1 CA 002383566 A CA002383566 A CA 002383566A CA 2383566 A CA2383566 A CA 2383566A CA 2383566 A1 CA2383566 A1 CA 2383566A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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Abstract
The invention relates to rubber mixtures containing a terpolymer (NSBR) based on an unsaturated olefinic nitrite, a vinyl aromatic compound and a conjugated diene, a non-polar rubber and a special mineral oil. The rubber mixtures according to the present invention have, in particular, an improved wet-skid behavior compared to rubber mixtures to which the conventional aromatic mineral oils have been added.
Description
Mo6789 Le A 35 013-lJS Rfllngb/NT _ 1 _ TERPOLYMERS AND RUBBER MIXTURES
CONTAINING 3PECIAh MINERALOILS
FIS-~D O~ TI IE INVENTION
The present invention rolatos to rubber mixtures containing a terpolymer (NSBR) based on an unsaturated oletinio nitr(lo, a vinyl aromatic cc~mpnund and a conjugated dlene, as well as a non-polar rubber and a special mineral ell.
~tACKOROUN,~OF THE 1NVENT10N
It is known for economic and technhl naasorrs iv add aromatic oils to styrene-butadiene rubbers or butardiene rubbers. By extending the rubbers with mineral oils, their prooesslng behavior, for example, can be improved without adversely affecting the physical properties of the rubbers.
'15 The aromatic oils used to data inr this purpose have the disadvantage licrwdvdr that they often contain constituents that are carcinogenic. Attempts have, thereforo, been made to find alternatives that dv not have a carcinogenic effect, for the aromatic oils used to date. It has nvw boon found that mineral oils containing c~ dimethyi sulfioxido :20 (DMS(7) extract (corrosponding to IP346 test method) in an amount of < 3 wt.% and are, thereforA, not rragardec! as carcinogenic, appear suitable for addition to a very wide range of rubbers. As representativPQ of such special mineral oils the following may brr rrrenliunad try wt~y of example:
mild extraction solvate (MES) as well as treated distillate aromatic extract 25 (TDAE). Suoh mineral oily fire marketed for exempts by Shell, Esso, Br and Nynas.
The disadvantage, however, is that rubbers to which the aforementioned special mineral oils such as TDAE and MES have hr~n added suffer a deterioration in quality. In particular as regards wet-skid 30 behavior. Therefore, this means that such rubber mixtures are not particularly suitable for use in producing, for example, tire troads.
I R a :~:~ u~~-us _2_ .R
SUMMARY OF THE INVEN,- TIN
Accordingly, the object of the present invention is to provide rubtrdr mixtures that oan be mixed and/or extended with non-caroinogenic mineral oils and that have comparable or better teohnica) qualities than rubber mixtures to which hitherto conventional aromatic mineral oils have been added. In particular, the nabber mixtures accorcling to the present Invention should have an improved wet-skid bAhavier.
This object has ber-sn actridvc~c~ by adding tarpolymers (NSBR) based on an unsaturated olefinic nitrite, a vinyl aromatic compound aryd a oonjugutod diono to rubber mixtures that do not con~in carcinogenic min~ral oils.
The present invention accordingly provides rubber mixtures comprising at least a) a non-polar rubber.
b) a terpolymer comprising an olefiinically unsaturated nilrild, a vinyl aromatic compound and a conjuga#ed diene, and c) a mineral oil that contains a DMSO oxtrr~at in ran amount of t3 wt.°~, the component a) being present in amounts of 1 to 88 parts by weight, the component b) being proesent in amounts of 1 to 98 parts by weight and the component c) being present In amounts of 1 to 5o parts ay weight, in each c;abc~ rc~frrrrdd iv the total amount of rubber.
DCTAILCD DCSCRiPTION OF THE INVENTION
Rubber mixtures are preferred in which the component a) is prosont in amounts of 5 to 95 parts by weight, preferably 20 to 80 parts by weight, the component b) is present in amounts of 5 to 95 parts by weight, preferably 2l7 tc~ 8Q parts by wAiflht, and the component c) is present In arnvunls of 5 Lv 40 parts by wetght. preferably 5 to 25 parts by weight, In each case with respect to the total drrrr,unt of ruwEror.
As non-polar rubbers, there may be used for the rubber mixtures according to the present invention, natural rubbers (NR) :as well a~
corresponding synthetic rubbers such as polybutadienes (BR), styrene-Le A 35 013-US
butadiene copolymers (SBR), polyisoprene rubbers (/R), isoprene-butadiene rubbers, isoprene-butadiene-styrene rubbers (S-SIBR) and ethylene-propylene-diene terpolymers (EPDM), preferably SBR, BR, IR
and NR. Most preferred are BR and SBR.
The aforementioned non-polar rubbers are generally known and are produced, for example, by free-radical emulsion polymerization, by free-radical solution polymerization, by anionic or cationic polymerization, or by polymerization with Ziegler-Natter catalysts.
Obviously, the aforementioned rubbers may be used individually or in arbitrary mixtures with one another in the rubber mixture according to the present invention. If different rubbers are mixed with one another, then the amount of the rubbers used is governed by, among other things, the respective intended use and application of the rubber mixture according to the present invention. The quantitative ratio and/or mixing ratio are therefore, suitably adapted thereto.
The terpolymer used as component b) in the rubber mixtures according to the present invention is based, as mentioned hereinbefore, on unsaturated olefinic nitrites, vinyl aromatic compounds and conjugated dienes.
As conjugated dienes, the following in particular are suitable: 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, 3,4-dimethyl-1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 4,5-diethyl-1,3-octadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene or mixtures of the aforementioned dienes. 1,3-butadiene and 2-methyl-1,3-butadiene are preferably used as conjugated dienes.
1,3-butadiene is more preferred.
As vinyl aromatic compounds, there may be mentioned those that contain 8 to 16 carbon atoms, such as styrene, a-methylstyrene, 2-methylstirene, 3-methylstirene, 4-methylstirene, 4-cyclohexylstirene, 4-p-toluenestirene, J,.e A y~,5 U13-US
_et_ p-chlorostyrend. p-brorrxmtyrond. 4-ldrl.-nulylalyrrrnr~. 1-vinylnaptrihaidnd and 2 vinylnaphthalene or mixtures theroof. Styrone i3 proferred.
As olefinioally un9atureted nitrites for the synth~eis of the terpolymena, the following may be used: acrylonitrilo, mothacrylonitrila, ethylacrylonitriiQ, crotonitrile and 2-pant~nenitrile or mixtures then~f.
AcrylonltrUe is preferred.
The optimum ratio of the aforem~ntlonad monomers in the terpolymer used accorclinc~ to the prosont invention moy easily be determined by appropriate preliminary experiments, the optimum mixing ratio being governed by, among other things, the respective intended use of the rubber mixtures according to the present invention.
The terpolymers to be used according to the present invention generally contain the conjugated dlenes In amounts of e.g. 40 to 89 wt.%.
the vinyl aromatic compounds in amounts of e.g. 10 to 40 wt.%, and the olefinirally unsaturated nitrites in amounts of e.g. 1 to 50 wt.%, the amounts of the individual components being made up to 100 wt.9~.
Preferably the conjugated dlenee are used in amounts of 40 to 80 wt.%, the vinyl aromatic compounds in amounts of 10 to 35 wt.%, and the Qlefinically unsaturatAd nitr(les in amounts of 10 to 40 wt.%.
depending on the amounts of the starting compounds that dre uaerl, the glass transition temperature of the terpolymers used according to the present invention is e.g. -60" to 0"C, preferably -45" to -15°C.
The N9BR terpolymers used according to the prosent invention are described in morc detail, for example, in EP-/1-537 640, U.S. Psatant No.
26 6,310,816 as well as U.S. Patent No. 5,225,479.
As component c) there are added to the rubber mixtures according to the present (nventhn, mlnAral nil chat cctntaln a DMSC extract of c3 wt.9~o and that are not considered tv be carcinogenic.
Preferably, the following ara used as mineral oils:
mild ration solvate (ME8), Le A 35 013-US
treated distillate aromatic extract (TDAE) as well as mineral oils such as naphthenic oils or hydrogenated naphthenic oils.
MES and TDAE are preferably used.
The chemical compositions of the aforementioned mineral oils used according to the present invention are known in the literature.
The mineral oils may be used individually or as mixtures with one another. The optimum mixing ratio can easily be determined by appropriate preliminary experiments.
Typical properties of MES oil and TDAE oil are given in the following Tables:
MES
Appearance pale brown clear liquid Density 15°C 907 kg/m3 ASTM 4502 Pour point 3°C ASTM D97 Viscosity 40C 200+/-30 mm2/sec.ASTM D445 Viscosity 100C 15+/-2 mm2/sec. ASTM D445 Refractive index 20C 1.500+/-0.005 ASTM D2159 Viscosity density constant 0.845+/-20 ASTM D2140 Carbon type: ASTM D2140 Aromatic 11-17%
Naphthenic 25-32%
Paraffinic 54-68%
Glass transition temperature -58+/-3C ASTM E1356-98 Flashpoint 220C min. ASTM D92 Water content 0.5% ASTM D6304-98a Content of polycyclic aromatic ounds2.90% max. 1P346 comp Le A 35 013-US
_g_ TDAE
Appearance pale brown liquid Density 15C 0.943 kg/m3 ASTM 4502 Pour point 0C max. ASTM D97 Viscosity 40C 400+/-30 mm2/sec.ASTM D445 Viscosity 100C 19+/-2 mm2/sec. ASTM D445 Refractive index 20C 1.520+/-0.005 ASTM D2159 Viscosity density constant 0.900+/-40 ASTM D2140 Carbon type: ASTM D2140 Aromatic 25-30%
Naphthenic 25-30%
Paraffinic 42-50%
Glass transition temperature -47+/-3C ASTM E1356-98 Flashpoint 220C min. ASTM D92 Water content 0.5% ASTM D6304-98a Content of polycyclic aromatic ounds2.90% max. /P346 comp Obviously, there may be added to the rubber mixtures according to the present invention, in addition to the aforementioned components a) to c) the following may also be added to the rubber mixtures, the known rubber auxiliary substances such as fillers, pigments, zinc oxide, stearic acid, vulcanization accelerators, vulcanization and/or crosslinking agents based on sulfur or peroxide, stabilizers, antioxidants, resins, oils, waxes as well as inhibitors.
Preferably, silicic acid and carbon black are added as fillers.
Precipitated silicic acids and finely particulate furnace carbon blacks are more preferred.
The fillers and the aforementioned rubber auxiliary substances are used in the conventional amounts and are known to the person skilled in the art.
Le A 35 013-US
The rubber mixtures according to the present invention may be produced by intensively mixing the individual components with one another in mixing units suitable for this purpose, such as rollers or kneaders. The order of addition of the individual components is not critical and may be arbitrarily chosen. Obviously, it is in this connection also possible to mix in the mineral oil to be used completely or partially before the individual components a) and b).
The rubber mixtures according to the present invention may be vulcanized in a conventional manner, the vulcanization process being determined by the respective intended application of the rubber mixtures.
The rubber mixtures according to the present invention may be used for the production of all types of vulcanizates, for example for the production of tire parts such as tire treads and sidewalls, or for the production of industrial rubber articles such as belts, straps, conveyor belts, floor coverings, mats, seals, shoe soles and hoses.
It is preferred to use the rubber mixtures according to the present invention in tire manufacture, in particular for tire treads.
In the following examples, the properties of the rubber mixtures according to the present invention, the comparison rubber mixtures and the vulcanizates produced therefrom were measured as follows:
(1 ) The polymer composition of the termonomer was determined by means of IR spectroscopy.
CONTAINING 3PECIAh MINERALOILS
FIS-~D O~ TI IE INVENTION
The present invention rolatos to rubber mixtures containing a terpolymer (NSBR) based on an unsaturated oletinio nitr(lo, a vinyl aromatic cc~mpnund and a conjugated dlene, as well as a non-polar rubber and a special mineral ell.
~tACKOROUN,~OF THE 1NVENT10N
It is known for economic and technhl naasorrs iv add aromatic oils to styrene-butadiene rubbers or butardiene rubbers. By extending the rubbers with mineral oils, their prooesslng behavior, for example, can be improved without adversely affecting the physical properties of the rubbers.
'15 The aromatic oils used to data inr this purpose have the disadvantage licrwdvdr that they often contain constituents that are carcinogenic. Attempts have, thereforo, been made to find alternatives that dv not have a carcinogenic effect, for the aromatic oils used to date. It has nvw boon found that mineral oils containing c~ dimethyi sulfioxido :20 (DMS(7) extract (corrosponding to IP346 test method) in an amount of < 3 wt.% and are, thereforA, not rragardec! as carcinogenic, appear suitable for addition to a very wide range of rubbers. As representativPQ of such special mineral oils the following may brr rrrenliunad try wt~y of example:
mild extraction solvate (MES) as well as treated distillate aromatic extract 25 (TDAE). Suoh mineral oily fire marketed for exempts by Shell, Esso, Br and Nynas.
The disadvantage, however, is that rubbers to which the aforementioned special mineral oils such as TDAE and MES have hr~n added suffer a deterioration in quality. In particular as regards wet-skid 30 behavior. Therefore, this means that such rubber mixtures are not particularly suitable for use in producing, for example, tire troads.
I R a :~:~ u~~-us _2_ .R
SUMMARY OF THE INVEN,- TIN
Accordingly, the object of the present invention is to provide rubtrdr mixtures that oan be mixed and/or extended with non-caroinogenic mineral oils and that have comparable or better teohnica) qualities than rubber mixtures to which hitherto conventional aromatic mineral oils have been added. In particular, the nabber mixtures accorcling to the present Invention should have an improved wet-skid bAhavier.
This object has ber-sn actridvc~c~ by adding tarpolymers (NSBR) based on an unsaturated olefinic nitrite, a vinyl aromatic compound aryd a oonjugutod diono to rubber mixtures that do not con~in carcinogenic min~ral oils.
The present invention accordingly provides rubber mixtures comprising at least a) a non-polar rubber.
b) a terpolymer comprising an olefiinically unsaturated nilrild, a vinyl aromatic compound and a conjuga#ed diene, and c) a mineral oil that contains a DMSO oxtrr~at in ran amount of t3 wt.°~, the component a) being present in amounts of 1 to 88 parts by weight, the component b) being proesent in amounts of 1 to 98 parts by weight and the component c) being present In amounts of 1 to 5o parts ay weight, in each c;abc~ rc~frrrrdd iv the total amount of rubber.
DCTAILCD DCSCRiPTION OF THE INVENTION
Rubber mixtures are preferred in which the component a) is prosont in amounts of 5 to 95 parts by weight, preferably 20 to 80 parts by weight, the component b) is present in amounts of 5 to 95 parts by weight, preferably 2l7 tc~ 8Q parts by wAiflht, and the component c) is present In arnvunls of 5 Lv 40 parts by wetght. preferably 5 to 25 parts by weight, In each case with respect to the total drrrr,unt of ruwEror.
As non-polar rubbers, there may be used for the rubber mixtures according to the present invention, natural rubbers (NR) :as well a~
corresponding synthetic rubbers such as polybutadienes (BR), styrene-Le A 35 013-US
butadiene copolymers (SBR), polyisoprene rubbers (/R), isoprene-butadiene rubbers, isoprene-butadiene-styrene rubbers (S-SIBR) and ethylene-propylene-diene terpolymers (EPDM), preferably SBR, BR, IR
and NR. Most preferred are BR and SBR.
The aforementioned non-polar rubbers are generally known and are produced, for example, by free-radical emulsion polymerization, by free-radical solution polymerization, by anionic or cationic polymerization, or by polymerization with Ziegler-Natter catalysts.
Obviously, the aforementioned rubbers may be used individually or in arbitrary mixtures with one another in the rubber mixture according to the present invention. If different rubbers are mixed with one another, then the amount of the rubbers used is governed by, among other things, the respective intended use and application of the rubber mixture according to the present invention. The quantitative ratio and/or mixing ratio are therefore, suitably adapted thereto.
The terpolymer used as component b) in the rubber mixtures according to the present invention is based, as mentioned hereinbefore, on unsaturated olefinic nitrites, vinyl aromatic compounds and conjugated dienes.
As conjugated dienes, the following in particular are suitable: 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, 3,4-dimethyl-1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 4,5-diethyl-1,3-octadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene or mixtures of the aforementioned dienes. 1,3-butadiene and 2-methyl-1,3-butadiene are preferably used as conjugated dienes.
1,3-butadiene is more preferred.
As vinyl aromatic compounds, there may be mentioned those that contain 8 to 16 carbon atoms, such as styrene, a-methylstyrene, 2-methylstirene, 3-methylstirene, 4-methylstirene, 4-cyclohexylstirene, 4-p-toluenestirene, J,.e A y~,5 U13-US
_et_ p-chlorostyrend. p-brorrxmtyrond. 4-ldrl.-nulylalyrrrnr~. 1-vinylnaptrihaidnd and 2 vinylnaphthalene or mixtures theroof. Styrone i3 proferred.
As olefinioally un9atureted nitrites for the synth~eis of the terpolymena, the following may be used: acrylonitrilo, mothacrylonitrila, ethylacrylonitriiQ, crotonitrile and 2-pant~nenitrile or mixtures then~f.
AcrylonltrUe is preferred.
The optimum ratio of the aforem~ntlonad monomers in the terpolymer used accorclinc~ to the prosont invention moy easily be determined by appropriate preliminary experiments, the optimum mixing ratio being governed by, among other things, the respective intended use of the rubber mixtures according to the present invention.
The terpolymers to be used according to the present invention generally contain the conjugated dlenes In amounts of e.g. 40 to 89 wt.%.
the vinyl aromatic compounds in amounts of e.g. 10 to 40 wt.%, and the olefinirally unsaturated nitrites in amounts of e.g. 1 to 50 wt.%, the amounts of the individual components being made up to 100 wt.9~.
Preferably the conjugated dlenee are used in amounts of 40 to 80 wt.%, the vinyl aromatic compounds in amounts of 10 to 35 wt.%, and the Qlefinically unsaturatAd nitr(les in amounts of 10 to 40 wt.%.
depending on the amounts of the starting compounds that dre uaerl, the glass transition temperature of the terpolymers used according to the present invention is e.g. -60" to 0"C, preferably -45" to -15°C.
The N9BR terpolymers used according to the prosent invention are described in morc detail, for example, in EP-/1-537 640, U.S. Psatant No.
26 6,310,816 as well as U.S. Patent No. 5,225,479.
As component c) there are added to the rubber mixtures according to the present (nventhn, mlnAral nil chat cctntaln a DMSC extract of c3 wt.9~o and that are not considered tv be carcinogenic.
Preferably, the following ara used as mineral oils:
mild ration solvate (ME8), Le A 35 013-US
treated distillate aromatic extract (TDAE) as well as mineral oils such as naphthenic oils or hydrogenated naphthenic oils.
MES and TDAE are preferably used.
The chemical compositions of the aforementioned mineral oils used according to the present invention are known in the literature.
The mineral oils may be used individually or as mixtures with one another. The optimum mixing ratio can easily be determined by appropriate preliminary experiments.
Typical properties of MES oil and TDAE oil are given in the following Tables:
MES
Appearance pale brown clear liquid Density 15°C 907 kg/m3 ASTM 4502 Pour point 3°C ASTM D97 Viscosity 40C 200+/-30 mm2/sec.ASTM D445 Viscosity 100C 15+/-2 mm2/sec. ASTM D445 Refractive index 20C 1.500+/-0.005 ASTM D2159 Viscosity density constant 0.845+/-20 ASTM D2140 Carbon type: ASTM D2140 Aromatic 11-17%
Naphthenic 25-32%
Paraffinic 54-68%
Glass transition temperature -58+/-3C ASTM E1356-98 Flashpoint 220C min. ASTM D92 Water content 0.5% ASTM D6304-98a Content of polycyclic aromatic ounds2.90% max. 1P346 comp Le A 35 013-US
_g_ TDAE
Appearance pale brown liquid Density 15C 0.943 kg/m3 ASTM 4502 Pour point 0C max. ASTM D97 Viscosity 40C 400+/-30 mm2/sec.ASTM D445 Viscosity 100C 19+/-2 mm2/sec. ASTM D445 Refractive index 20C 1.520+/-0.005 ASTM D2159 Viscosity density constant 0.900+/-40 ASTM D2140 Carbon type: ASTM D2140 Aromatic 25-30%
Naphthenic 25-30%
Paraffinic 42-50%
Glass transition temperature -47+/-3C ASTM E1356-98 Flashpoint 220C min. ASTM D92 Water content 0.5% ASTM D6304-98a Content of polycyclic aromatic ounds2.90% max. /P346 comp Obviously, there may be added to the rubber mixtures according to the present invention, in addition to the aforementioned components a) to c) the following may also be added to the rubber mixtures, the known rubber auxiliary substances such as fillers, pigments, zinc oxide, stearic acid, vulcanization accelerators, vulcanization and/or crosslinking agents based on sulfur or peroxide, stabilizers, antioxidants, resins, oils, waxes as well as inhibitors.
Preferably, silicic acid and carbon black are added as fillers.
Precipitated silicic acids and finely particulate furnace carbon blacks are more preferred.
The fillers and the aforementioned rubber auxiliary substances are used in the conventional amounts and are known to the person skilled in the art.
Le A 35 013-US
The rubber mixtures according to the present invention may be produced by intensively mixing the individual components with one another in mixing units suitable for this purpose, such as rollers or kneaders. The order of addition of the individual components is not critical and may be arbitrarily chosen. Obviously, it is in this connection also possible to mix in the mineral oil to be used completely or partially before the individual components a) and b).
The rubber mixtures according to the present invention may be vulcanized in a conventional manner, the vulcanization process being determined by the respective intended application of the rubber mixtures.
The rubber mixtures according to the present invention may be used for the production of all types of vulcanizates, for example for the production of tire parts such as tire treads and sidewalls, or for the production of industrial rubber articles such as belts, straps, conveyor belts, floor coverings, mats, seals, shoe soles and hoses.
It is preferred to use the rubber mixtures according to the present invention in tire manufacture, in particular for tire treads.
In the following examples, the properties of the rubber mixtures according to the present invention, the comparison rubber mixtures and the vulcanizates produced therefrom were measured as follows:
(1 ) The polymer composition of the termonomer was determined by means of IR spectroscopy.
(2) The Mooney viscosity of the rubbers was determined according to DIN 53523.
(3) The tensile strength of the vulcanizates was determined according to D I N 53504.
(4) The elongation at break of the vulcanizates was determined according to DIN 53504.
(5) The modulus of the vulcanizates at 100% and 300% elongation was determined according to DIN 53504.
Le A 35 013-US
_g_ (6) The hardness of the vulcanizates at 23°C and 70°C was determined according to DIN 53505.
Le A 35 013-US
_g_ (6) The hardness of the vulcanizates at 23°C and 70°C was determined according to DIN 53505.
(7) The rebound elasticity at 23°C and 70°C was determined according to DIN 53512.
(8) The abrasion of the vulcanizates was determined according to DIN
53516.
53516.
(9) The tan b values of the vulcanizates was determined according to DIN 53513.
EXAMPLES
The following components were used for the comparison rubber mixtures 1 and 2 as well as for the rubber mixtures 1, 2 and 3 according to the present invention:
SBR 1712 (Krynol~ 1712, emulsion SBR, 23.5% styrene, 37.5% aromatic oil, manufacturer Bayer Elastomeres), SBR 1712 (emulsion SBR, 23.5% styrene, 37.5% MES oil), SBR 1513 (Cariflex~ 1513, emulsion SBR, 40% styrene, manufacturer DOW) NSBR (rubber produced by emulsion polymerization, 58.5% butadiene, 20.3% styrene and 21.1 % acrylonitrile, Mooney viscosity 49), Renopal~ 450 (aromatic mineral oil/plasticizer, manufacturer Fuchs Chemie), MES oil (Catenex SNR~, manufacturer Shell) Corax~ N339 (carbon black, manufacturer Degussa Huls AG), Vulkasil S (silicic acid, Bayer AG), Si 69~ (bis-3-(triethoxysilylpropyl)tetrasulfide, manufacturer Degussa AG), Stearic acid Zn0 (zinc oxide), Sulfur IPPD (Vulcanox~ 4010, N-isopropyl-N'-phenyl-p-phenylenediamine, manufacturer Bayer AG) Le A 35 013-US
_g_ 6PPD (Vulcanox° 4020 N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, manufacturer Bayer AG), DPB (Vulkacit~ D, diphenylguanidine, manufacturer Bayer AG), CBS (Vulkacit~ CZ/C N-cyclohexyl-2-benzothiazylsulfenamide, manufacturer Bayer AG).
The individual parts by weight of the components are given in Tables 1 and 2.
The components were mixed in a kneader (Vllerner & Pfleiderer GK
1.5) at 50 r.p.m. The kneading temperature was 60°C. The vulcanization accelerators were mixed in on a roller.
The results of the tests are given in Tables 1 and 2.
Table 1 (Carbon black mixture) 1* 2* 3 37.5% 37.5% 37.5%
Aromatic MES Oil MES Oil with Oil NSBR
SBR 1712 (37.5% aromatic110 0 0 oil) SBR 1712 37.5% MES oil 0 110 110 NSBR 20% ACN 0 0 20 Aromatic oil 7:5 0 0 MES oil 0 7.5 7.5 N-339 Carbon black 50 50 50 Stearic acid 2 2 2 Zinc oxide 3 3 3 Sulfur 2 2 2 CBS 1.5 1.5 1.5 DPG ~ 0.2 I 0.2 ~2 * comparison Le A 35 013-US
EXAMPLES
The following components were used for the comparison rubber mixtures 1 and 2 as well as for the rubber mixtures 1, 2 and 3 according to the present invention:
SBR 1712 (Krynol~ 1712, emulsion SBR, 23.5% styrene, 37.5% aromatic oil, manufacturer Bayer Elastomeres), SBR 1712 (emulsion SBR, 23.5% styrene, 37.5% MES oil), SBR 1513 (Cariflex~ 1513, emulsion SBR, 40% styrene, manufacturer DOW) NSBR (rubber produced by emulsion polymerization, 58.5% butadiene, 20.3% styrene and 21.1 % acrylonitrile, Mooney viscosity 49), Renopal~ 450 (aromatic mineral oil/plasticizer, manufacturer Fuchs Chemie), MES oil (Catenex SNR~, manufacturer Shell) Corax~ N339 (carbon black, manufacturer Degussa Huls AG), Vulkasil S (silicic acid, Bayer AG), Si 69~ (bis-3-(triethoxysilylpropyl)tetrasulfide, manufacturer Degussa AG), Stearic acid Zn0 (zinc oxide), Sulfur IPPD (Vulcanox~ 4010, N-isopropyl-N'-phenyl-p-phenylenediamine, manufacturer Bayer AG) Le A 35 013-US
_g_ 6PPD (Vulcanox° 4020 N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, manufacturer Bayer AG), DPB (Vulkacit~ D, diphenylguanidine, manufacturer Bayer AG), CBS (Vulkacit~ CZ/C N-cyclohexyl-2-benzothiazylsulfenamide, manufacturer Bayer AG).
The individual parts by weight of the components are given in Tables 1 and 2.
The components were mixed in a kneader (Vllerner & Pfleiderer GK
1.5) at 50 r.p.m. The kneading temperature was 60°C. The vulcanization accelerators were mixed in on a roller.
The results of the tests are given in Tables 1 and 2.
Table 1 (Carbon black mixture) 1* 2* 3 37.5% 37.5% 37.5%
Aromatic MES Oil MES Oil with Oil NSBR
SBR 1712 (37.5% aromatic110 0 0 oil) SBR 1712 37.5% MES oil 0 110 110 NSBR 20% ACN 0 0 20 Aromatic oil 7:5 0 0 MES oil 0 7.5 7.5 N-339 Carbon black 50 50 50 Stearic acid 2 2 2 Zinc oxide 3 3 3 Sulfur 2 2 2 CBS 1.5 1.5 1.5 DPG ~ 0.2 I 0.2 ~2 * comparison Le A 35 013-US
Vulcanizate Properties1 * 2* 3 37.5% 37.5% 37.5%
Aromatic MES Oil MES Oil with NSBR
Oil Tensile stren th MPa 22.9 17.8 16.5 Elon ation at break 683 573 533 %
M 100% MPa 1.2 1.1 1.2 M 300% MPa 5.6 6 6.2 Hardness 23C 54 53 54 Hardness 70C 49 49 48 Elasticit 23C 33 38 33 Elasticit 70C 49 51 53 DIN abrasion mm 170 124 108 Tan delta 0C 0.424 0.326 0.460 Tan delta 60C 0.162 0.148 0.147 The person skilled in the art knows that a high tan b value at 0°C
denotes a good wet-skid behavior, while a low tan 8 value at 60°C
denotes a low rolling resistance.
Example 1 (comparison example) contains 37.5% aromatic oil. If the aromatic oil is replaced by MES oil in Example 2 (comparison example), the wet-skid behavior deteriorates (lower tan 8 value at 0°C). On the other hand, the abrasion resistance and rolling resistance (higher tan 8 value at 60°C) are improved. In Example 3, according to the present invention, the high styrene content SBR 1513 is replaced by the terpolymer (NSBR).
Accordingly the abrasion resistance, wet-skid behavior and the rolling resistance are significantly improved compared to Example 1 (comparison example). Compared to Example 2 (comparison example), at the same rolling resistance, the wet-skid behavior and the rolling resistance are significantly improved. The rubber mixtures according to the present invention are clearly superior to those of the prior art.
Le A 35 013-US
Aromatic MES Oil MES Oil with NSBR
Oil Tensile stren th MPa 22.9 17.8 16.5 Elon ation at break 683 573 533 %
M 100% MPa 1.2 1.1 1.2 M 300% MPa 5.6 6 6.2 Hardness 23C 54 53 54 Hardness 70C 49 49 48 Elasticit 23C 33 38 33 Elasticit 70C 49 51 53 DIN abrasion mm 170 124 108 Tan delta 0C 0.424 0.326 0.460 Tan delta 60C 0.162 0.148 0.147 The person skilled in the art knows that a high tan b value at 0°C
denotes a good wet-skid behavior, while a low tan 8 value at 60°C
denotes a low rolling resistance.
Example 1 (comparison example) contains 37.5% aromatic oil. If the aromatic oil is replaced by MES oil in Example 2 (comparison example), the wet-skid behavior deteriorates (lower tan 8 value at 0°C). On the other hand, the abrasion resistance and rolling resistance (higher tan 8 value at 60°C) are improved. In Example 3, according to the present invention, the high styrene content SBR 1513 is replaced by the terpolymer (NSBR).
Accordingly the abrasion resistance, wet-skid behavior and the rolling resistance are significantly improved compared to Example 1 (comparison example). Compared to Example 2 (comparison example), at the same rolling resistance, the wet-skid behavior and the rolling resistance are significantly improved. The rubber mixtures according to the present invention are clearly superior to those of the prior art.
Le A 35 013-US
Table 2 (Rubber/silicic acid mixture) 4* 5* 6 37.5% 37.5% 37.5%
Aromatic MES Oil MES Oil Oil SBR 1712 (37.5% aromatic110 0 0 oil) SBR 1712 (37.5% MES 0 110 110 oil) NSBR 20% ACN 0 0 20 Aromatic oil 7.5 0 0 MES oil 0 7.5 7.5 N-339 Carbon black 25 25 25 Vulkasil S 25 25 25 Si69 2 2 2 Stearic acid 2 2 ' 2 Zinc oxide 3 3 3 Sulfur 2 2 2 CBS 1.5 1.5 1.5 DPG 0.2 0.2 0.2 * comparison Le A 35 013-US
Aromatic MES Oil MES Oil Oil SBR 1712 (37.5% aromatic110 0 0 oil) SBR 1712 (37.5% MES 0 110 110 oil) NSBR 20% ACN 0 0 20 Aromatic oil 7.5 0 0 MES oil 0 7.5 7.5 N-339 Carbon black 25 25 25 Vulkasil S 25 25 25 Si69 2 2 2 Stearic acid 2 2 ' 2 Zinc oxide 3 3 3 Sulfur 2 2 2 CBS 1.5 1.5 1.5 DPG 0.2 0.2 0.2 * comparison Le A 35 013-US
Vulcanizate Properties4* 5* 6 37.5% 37.5% 37.5%
Aromatic MES Oil MES Oil with NSBR
Oil Tensile stren th 23.9 22.2 15.5 MPa Elon ation at break 745 716 588 %
M 100% MPa 1.1 1 1,1 M 300% MPa 4.5 4.3 4.7 Hardness 23C 53 50 51 Hardness 70C 47 45 45 Elasticit 23C 36 39 35 Elasticit 70C 52 53 53 DIN abrasion mms 211 172 132 Tan delta 0C 0.423 0.309 0.435 Tan delta 60C 0.151 0.133 0.136 The person skilled in the art knows that mixtures of various fillers can also be used. In these cases too, the rubbers according to the present invention are superior to the prior art. In this connection, the substitution of the aromatic oil by MES oil leads to a deterioration in the wet-skid behavior (compare Examples 4 and 5, both comparison examples). In Example 6 according to the present invention, the replacement of ESBR 1513 by the terpolymer (NSBR) leads to a marked improvement in the properties of abrasion resistance, wet-skid behavior and rolling resistance. Compared to Example 4 (comparison example), the abrasion resistance, wet-skid behavior (higher tan 8 value at 0°C) and rolling resistance.(lower tan 8 value at 60°C) and compared to Example (comparison example) the abrasion resistance and wet-skid behavior are all improved. The rubber mixtures according to the present invention are clearly superior to those of the prior art.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Aromatic MES Oil MES Oil with NSBR
Oil Tensile stren th 23.9 22.2 15.5 MPa Elon ation at break 745 716 588 %
M 100% MPa 1.1 1 1,1 M 300% MPa 4.5 4.3 4.7 Hardness 23C 53 50 51 Hardness 70C 47 45 45 Elasticit 23C 36 39 35 Elasticit 70C 52 53 53 DIN abrasion mms 211 172 132 Tan delta 0C 0.423 0.309 0.435 Tan delta 60C 0.151 0.133 0.136 The person skilled in the art knows that mixtures of various fillers can also be used. In these cases too, the rubbers according to the present invention are superior to the prior art. In this connection, the substitution of the aromatic oil by MES oil leads to a deterioration in the wet-skid behavior (compare Examples 4 and 5, both comparison examples). In Example 6 according to the present invention, the replacement of ESBR 1513 by the terpolymer (NSBR) leads to a marked improvement in the properties of abrasion resistance, wet-skid behavior and rolling resistance. Compared to Example 4 (comparison example), the abrasion resistance, wet-skid behavior (higher tan 8 value at 0°C) and rolling resistance.(lower tan 8 value at 60°C) and compared to Example (comparison example) the abrasion resistance and wet-skid behavior are all improved. The rubber mixtures according to the present invention are clearly superior to those of the prior art.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (8)
1. A rubber mixture comprising a) a non-polar rubber, b) a terpolymer comprising an olefinically unsaturated nitrile, a vinyl aromatic compound and a conjugated diene, and c) a mineral oil that contains a DMSO extract of <=3 wt.%, the component a) being present in amounts of 1 to 99 parts by weight, the component b) in amounts of 1 to 99 parts by weight and the component c) in amounts of 1 to 50 parts by weight, in each case referred to the total amount of rubber.
2. A rubber mixture according to claim 1, wherein component a) is present in an amount of 5 to 95 parts by weight, component b) in an amount of 5 to 95 parts by weight and component c) in an amount of 5 to 40 parts by weight in the rubber mixture.
3. A rubber mixture according to claim 1 or 2, wherein said non-polar rubber is selected from the group consisting of natural rubbers, polybutadiene rubbers, styrene-butadiene rubbers, polyisoprene rubbers, isoprene-butadiene rubbers, isoprene-butadiene-styrene rubbers, and ethylene-propylene dime rubbers.
4. A rubber mixture according to claim 1, 2 or 3, wherein the terpolymer is built up from styrene, acrylonitrile and 1,3-butadiene.
5. A rubber mixture according to claim 1, 2 or 3, wherein the terpolymer is built up from styrene, acrylonitrile and 2-methyl-1,3-butadiene.
6. A rubber mixture according to claim 1, 2 or 3, wherein the terpolymer is built up from styrene, acrylonitrile and a mixture of 1,3-butadiene and 2-methyl-1,3-butadiene.
7. An industrial rubber article comprising a rubber mixture according to any one of claims 1 to 6.
8. An industrial rubber article according to claim 7, which article is a tire or a structural part of a tire.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10121161A DE10121161A1 (en) | 2001-04-30 | 2001-04-30 | Rubber mixture, useful for the production of tires and molded articles, comprises a non-polar rubber, a terpolymer and a mineral oil having DMSO extract of no greater than 3 wt.%. |
| DE10121161.9 | 2001-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2383566A1 true CA2383566A1 (en) | 2002-10-30 |
Family
ID=7683269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002383566A Abandoned CA2383566A1 (en) | 2001-04-30 | 2002-04-26 | Terpolymers and rubber mixtures containing special mineral oils |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20020198296A1 (en) |
| EP (1) | EP1254920A1 (en) |
| JP (1) | JP2002338754A (en) |
| KR (1) | KR20020084412A (en) |
| BR (1) | BR0201512A (en) |
| CA (1) | CA2383566A1 (en) |
| DE (1) | DE10121161A1 (en) |
| MX (1) | MXPA02004284A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100437687B1 (en) * | 2001-03-27 | 2004-06-26 | 금호타이어 주식회사 | Dispersion-Improved Silica-filled SBR compounds Containing NSBR for Tire |
| US6939910B2 (en) † | 2001-12-28 | 2005-09-06 | Bridgestone Corporation | Rubber composition |
| JP4275388B2 (en) * | 2002-11-15 | 2009-06-10 | 株式会社ブリヂストン | Tread rubber composition and tire |
| JP2005002295A (en) * | 2003-06-16 | 2005-01-06 | Bridgestone Corp | Rubber composition for tire and tire |
| US7193004B2 (en) * | 2003-06-30 | 2007-03-20 | The Goodyear Tire & Rubber Company | Pneumatic tire having a component containing low PCA oil |
| US6977276B2 (en) | 2003-12-15 | 2005-12-20 | The Goodyear Tire & Rubber Company | Oil extended rubber and composition containing low PCA oil |
| US6984687B2 (en) | 2004-01-19 | 2006-01-10 | The Goodyear Tire & Rubber Company | Oil extended rubber and composition containing low PCA oil |
| US20050272850A1 (en) * | 2004-06-03 | 2005-12-08 | Jois Yajnanarayana H | Process for the preparation of rubber extender oil compositions |
| US7906602B2 (en) * | 2004-12-30 | 2011-03-15 | The Goodyear Tire & Rubber Company | Tread cap composition |
| US7714041B2 (en) * | 2004-12-30 | 2010-05-11 | The Goodyear Tire & Rubber Company | Method of increasing plasticity of tread composition |
| US7456233B2 (en) | 2005-02-16 | 2008-11-25 | Nordson Corporation | Adhesive composition |
| BRPI0614658A2 (en) * | 2005-07-29 | 2016-08-23 | Pirelli | tire, tread crosslinkable elastomeric composition, and crosslinked manufactured article |
| JP5361270B2 (en) * | 2008-07-25 | 2013-12-04 | 住友ゴム工業株式会社 | Rubber composition and tire using the same |
| BRPI0819543A8 (en) | 2008-12-12 | 2015-09-08 | Dow Global Technologies Inc | COMPOSITION, METHOD FOR PRODUCING THE COMPOSITION AND ARTICLE |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US522479A (en) * | 1894-07-03 | Electrode for secondary batteries | ||
| US4146277A (en) * | 1978-06-29 | 1979-03-27 | Santoro Dario S | Desiccant cap |
| EP0035256B1 (en) * | 1980-03-04 | 1983-07-13 | Siemens Aktiengesellschaft | Getter body and process for its manufacture |
| US4963788A (en) * | 1988-07-14 | 1990-10-16 | Planar Systems, Inc. | Thin film electroluminescent display with improved contrast |
| DE3837047A1 (en) * | 1988-10-31 | 1990-05-03 | Continental Ag | TREAD STRIP MIXTURE FOR VEHICLE AIR TIRES |
| US5304419A (en) * | 1990-07-06 | 1994-04-19 | Alpha Fry Ltd | Moisture and particle getter for enclosures |
| US5225479A (en) * | 1991-10-17 | 1993-07-06 | The Goodyear Tire & Rubber Company | Polymers derived from a conjugated diolefin, a vinyl-substituted aromatic compound, and olefinically unsaturated nitrile |
| JPH09148066A (en) * | 1995-11-24 | 1997-06-06 | Pioneer Electron Corp | Organic electroluminescent element |
| EP0940462A4 (en) * | 1997-06-27 | 2005-03-02 | Bridgestone Corp | Improved high-aromatic oil, and rubber composition and oil extended synthetic rubber both prepared by using said high aromatic oil |
| WO2002020632A1 (en) * | 2000-09-08 | 2002-03-14 | Bayer Aktiengesellschaft | Quaternary polymers with functional amine groups |
-
2001
- 2001-04-30 DE DE10121161A patent/DE10121161A1/en not_active Withdrawn
-
2002
- 2002-04-17 EP EP02008196A patent/EP1254920A1/en not_active Withdrawn
- 2002-04-25 US US10/132,053 patent/US20020198296A1/en not_active Abandoned
- 2002-04-26 JP JP2002127227A patent/JP2002338754A/en active Pending
- 2002-04-26 CA CA002383566A patent/CA2383566A1/en not_active Abandoned
- 2002-04-29 MX MXPA02004284A patent/MXPA02004284A/en not_active Application Discontinuation
- 2002-04-29 KR KR1020020023322A patent/KR20020084412A/en not_active Application Discontinuation
- 2002-04-30 BR BR0201512-9A patent/BR0201512A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA02004284A (en) | 2002-11-14 |
| EP1254920A1 (en) | 2002-11-06 |
| DE10121161A1 (en) | 2002-10-31 |
| BR0201512A (en) | 2003-06-10 |
| JP2002338754A (en) | 2002-11-27 |
| KR20020084412A (en) | 2002-11-07 |
| US20020198296A1 (en) | 2002-12-26 |
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